Shale Hydration Inhibition Characteristics and Mechanism of A New Amine-Based Additive in Water-Based Drilling Uids
Shale Hydration Inhibition Characteristics and Mechanism of A New Amine-Based Additive in Water-Based Drilling Uids
Shale Hydration Inhibition Characteristics and Mechanism of A New Amine-Based Additive in Water-Based Drilling Uids
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Article history: In this work, shale hydration Inhibition performance of tallow amine ethoxylate as a shale stabilizer
Received 25 September 2016 in water based drilling fluid, was investigated through these tests: bentonite hydration inhibition
Accepted 15 May 2017 test, bentonite sedimentation test, drill cutting recovery test, dynamic linear swelling test, wetta-
bility test, isothermal water adsorption test, and zeta potential test. The results showed that
Keywords: bentonite particles are not capable of being hydrated or dispersed in the mediums containing
Drilling fluids
tallow amine ethoxylate; tallow amine ethoxylate had shown a comparable and competitive in-
Dynamic linear swelling
hibition performance with potassium chloride as a common shale stabilizer in drilling industry.
Hydrogen bond
Mechanism
Some amine functional groups exist in tallow amine ethoxylate structure which are capable of
Shale stabilizer forming hydrogen bonding with surfaces of bentonite particles. This phenomenon decreased the
Tallow amine ethoxylate water adsorption on bentonite particles' surfaces which results in reduction of swelling. Tallow
Wettability amine ethoxylate is also compatible with other common drilling fluid additives.
Zeta potential Copyright © 2017, Southwest Petroleum University. Production and hosting by Elsevier B.V. on
Amine-based additive behalf of KeAi Communications Co., Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction the drilling fluid designers in recent years [4,5]. In most recent
researches, amines and their derivatives are of high interest to
A large part of underground formations consists of shaly rocks the researchers because of their sufficiency in controlling the
which face with swelling and disintegration when meeting the shale hydration and capability to extend their specification to
aqueous phase of drilling fluids. This event causes the wellbore almost any drilling operation conditions [6,7]. Qu et al. (2009)
washouts and drill string sticking in the borehole, wasting 1 synthesized polyoxyalkyleneamine (POAM) and investigated its
billion USD per year worldwide during the drilling operations inhibitive properties to Na-montmorillonite. Based on their re-
[1e3]. Drilling fluid designers are always seeking for high per- sults, POAM is completely water soluble, low toxic and
formance drilling fluids which are resistant to shale hydration compatible with other common drilling fluid additives. The re-
and disintegration, so they are more willing to use oil-based action between POAM molecules and clay minerals can involve
drilling fluids. But this sort of drilling fluids also has severe several mechanisms including hydrogen bonding and compete
degenerative effects on the environment in addition to its high with water molecules for reactive sites [1]. A new modified
operation and disposal costs. This makes them less desirable to polyethylene glycol (M-PEG) was introduced by Souza et al.
(2010) as a new shale inhibitor additive which could adsorbed
via hydrogen bonding on the clay particles' surfaces. It had much
greater effect on reducing the water uptake by the clays and
* Corresponding author. increasing their stabilities than those of polyethylene glycol [8].
E-mail address: pezhman.barati1987@gmail.com (P. Barati). The ability of poly(oxypropylene)diamine in suppressing the
Peer review under responsibility of Southwest Petroleum University. montmorillonite hydration was investigated by Wang et al.
(2011). They showed that poly(oxypropylene)diamine adsorbed
on particle surfaces via hydrogen boning and could form a hy-
Production and Hosting by Elsevier on behalf of KeAi
drophobic shell around them, and in some cases intercalate into
the montmorillonite interlayers which results in clay swelling
http://dx.doi.org/10.1016/j.petlm.2017.05.003
2405-6561/Copyright © 2017, Southwest Petroleum University. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
P. Barati et al. / Petroleum 3 (2017) 476e482 477
that PEDA stabilized shales by exchanging protonated dia- Product KETALLO15 (Tallow
mmonium ion to native sodium ions and expelled the water Amine Ethoxylate)
molecules out of the clay galleries which could bind the plates Appearance at 25 C Brownish Liquid
pH 9.8
together and improve their hydrophobicity against the water Molecular weight (g/mole) 910.7
molecules [4]. Poly(oxyprolylene)-amidoamine (POAA), a new Specific gravity at 25 C 1.023
counteractive agent, was examined by Zhong (2012) in order to Freezing/Melting point ( C) 7
neutralize the negatively charged sites of clay minerals which Boiling point ( C) >260
Total amine value (mg KOH/g) 61.6
make them more hydrophobic and stable against hydration [2].
Water (wt%) 0.08
Other new introduced amine-based additives could be referred Solubility in water Soluble
to bis(hexamethylen)triamine (BHMT) and dopamine (DA) [6,7].
Recently, Nano additives were used to improve the sealing ability
of muds during drilling through shaly formations by plugging of
2.2. Methods
pore throats and micro fractures [10,11]. Some researchers have
turned to investigate the performances of plant-based additives
2.2.1. Bentonite hydration inhibition test
such as horse tail in inhibiting the shaly formations against hy-
To assess the inhibition performance of KETALO15 against the
dration and disintegration [12].
bentonite hydration in aqueous phases, the bentonite hydration
In this work, shale hydration inhibition performance of tallow
inhibition test has been used. In this test, at first, the aqueous
amine ethoxylate along with its mechanisms have been inves-
solutions of KETALO15 with concentrations of 0, 0.5, 2 and 3 wt%
tigated through bentonite hydration inhibition, bentonite sedi-
have been prepared and then 10 wt% bentonite powder has been
mentation, hot rolling shale particle disintegration, dynamic
added, mixed and aged at atmospheric conditions for 24 h. Then
linear swelling, wettability alteration, isothermal water adsorp-
their filtration and rheological properties (i.e. yield point,
tion, and zeta potential measurement tests. Also the compati-
apparent and plastic viscosities) have been obtained using API
bility of tallow amine ethoxylate with other common drilling
low pressureelow temperature filter press and 35SA Fann rota-
fluid additives has been checked using drilling fluid making tests.
tional viscometer respectively, according to API recommended
practice on the rheology and hydraulic of oil-well drilling fluids
2. Materials and methods [15]. At the last part, inhibition performance of KETALO15 has
been compared with potassium chloride as a common shale
2.1. Materials stabilizer.
Tallow amine ethoxylate (CAS No. 61791-26-2) with chemical 2.2.2. Bentonite sedimentation test
name of tallow amine polyethylene glycol ether has been pur- Instability of dispersed bentonite particles in aqueous me-
chased from Kimyagaran Chemical Industries Company. The diums containing KETALO15 has been determined via bentonite
theoretical structure of this tertiary amine has been shown in sedimentation test. In this test, 3 wt% bentonite powder has been
Fig. 1. This polyamine is known as KETALO (trade name) and is a added to KETALO15 aqueous solutions with concentrations of 0,
non-ionic surfactant with a certain number of ethylene oxide 1, 2 and 3 wt%, mixed thoroughly using magnetic stirrer, poured
unites (EOn). In this study, KETALO with EO15 (KETALO15) has into the glass test tubes and kept in static-atmospheric condi-
been used. This kind of polyamine is cationic in nature because of tions for 24 h. Then, by measuring the distance from the clearly
existence of amine groups in its molecules structure, which can formed horizontal interference (between sediment and super-
be protonated [13]. KETALO15 properties presented by the natant) to test tube cap (h) and dividing it by internal length of
company has been summarized in Table 1. test tube (H), the ratio h/H can be calculated and plotted for each
Bentonite with high percentage of sodium montmorillonite test tubes containing different KETALO15 concentrations. Finally,
has been purchased from Pars Drilling Fluid Company, Tehran, the h/H ratios have been compared to those of potassium chlo-
Iran. The drilling cuttings have been obtained from Asmari for- ride as a common shale stabilizer.
mation of Maroon oilfield in southwest of Iran, well number 281,
and in depth of 4001e4008 m. Bentonite and drilling cuttings' 2.2.3. Compatibility test
CECs (Cation Exchange Capacities) (CEC) were have been deter- In order to investigate the compatibility of KETALO15 with
mined to be 18 and 3 mmol/g respectively, by sodium acetate the other common drilling fluid additives, two different formu-
method according to ISRIC soil analysis procedures [14]. Potas- lated drilling fluids have been selected (Table 2). Then the effects
sium hydroxide and potassium chloride have been supplied by of 2 wt% KETALO15 addition on their rheological and filtration
Merck Company, Germany. Other drilling fluid additives (PAC-LV,
PAC-R, starch-HV, PHPA, Xanthan gum, anti-foam, biocide, and
barite) have been purchased from Pars Drilling Fluids Company, Table 2
Tehran, Iran. All materials have been used without any further Test fluid formulation used in compatibility test.
Base drilling fluid Distilled water (450 ml), PAC-LV (2.57 g), Starch-HV
(10.28 g), Xanthan gum (1.54 g), Antifoam (0.2 ml),
Biocide (0.5 ml), Barite (up to 1.078 g/ml), Potassium
hydroxide (up to pH 9).
High performance Distilled water (450 ml), PAC-LV (2.57 g), PHPA (1.14
drilling fluid g), PAC-R (1.28 g), Starch-HV (10.28 g), Xanthan gum
(1.54 g), Potassium chloride (21 g), Antifoam (0.2 ml),
Biocide (0.5 ml), Barite (up to 1.078 g/ml), Potassium
hydroxide (up to pH 9).
Fig. 1. Theoretical structure of tallow amine ethoxylate [13].
478 P. Barati et al. / Petroleum 3 (2017) 476e482
properties have been determined. For this purpose, drilling fluids formations [2]. In this test, the effect of KETALO15 adsorption on
have been aged at 70 C using hot rolling oven (with the speed of the tendency reduction of bentonite particles' surfaces to water
22 rpm) for 4 h. Then their filtration and rheological properties molecules has been investigated. To do so, an aqueous bentonite
(i.e. yield point, 10 s and 10 min gel strengths, apparent and dispersion with concentration of 1.5 wt% has been prepared and
plastic viscosities) have been determined according to API rec- left for 24 h at atmospheric conditions. Then the prepared
ommended practice on the rheology and hydraulic of oil-well dispersion has been split into two parts. One part has been left
drilling fluids [15]. without any further treatment (blank dispersion) and the other
part has been treated by the addition of KETALO15 at 2 wt%
2.2.4. Hot rolling shale particles disintegration test concentrations (modified dispersion). Then, both parts have
Hot rolling shale particles disintegration test has been been centrifuged at 6000 rpm for 30 min. Sediments have been
employed to evaluate the inhibition performance of KETALO15 in collected, and oven has been dried at 105 C for 24 h, pulverized
preventing shale cuttings from hydration, disintegration and and screened by sieve mesh no. 200. 1 g of each sediment has
dispersion in (or to) the aqueous phase of drilling fluids ac- been left in a well-sealed desiccators containing distilled water
cording to API recommended practice of standard procedure for at the bottom (water activity of unit). After 11 days, the amount
laboratory testing drilling fluids [16]. In this test, 10 g sized shale of adsorbed water molecules has been calculated based on the
drill cuttings (between 2 and 4 mm) have been in contact with mass changes in atmospheric conditions.
drilling fluid at 70 C in hot rolling oven aging cells (with the
speed of 22 rpm). After 16 h, the recovery of drill cuttings (ratio
2.2.8. Zeta potential measurement test
of final oven dried weight to its initial weight) over mesh 35 has
Some of shale stabilizers will adsorb the negatively charged
been determined.
clay particles and affect their surface charge density and colloidal
stability. Colloidal stability reduction of clay particles can lead
2.2.5. Dynamic linear swelling test (DLST)
into increasing their durability against hydration and disinte-
This test has been used to investigate the effect of KETALO15
gration. In this test, effect of KETALO15 adsorption on the
on the bentonite wafers linear swelling which were in contact
colloidal stability of the well-dispersed bentonite particles has
with different test fluids at low (26 C) and elevated (65 C)
been studied. To do so, KETALO15 has been added to an aqueous
temperatures. In this test, 9.5 g bentonite wafers (with 28.3 mm
bentonite dispersion with concentration of 0.5 wt%, which lea-
diameter) have been produced under 27.58 MPa (4000 psi) for
ded into different KETALO15 concentrations. After shaking for
2 h using hydraulic compactor, and then their initial thickness
24 h, zeta potential of all samples has been measured at atmo-
have been measured using caliper (with accuracy of 0.01 mm).
spheric conditions using zeta potential analyzer (Zetasizer Nano
Then, the prepared bentonite wafers have been left in contact
ZS, Malvern Instrument Ltd.).
with test fluids for 4000 min in the dynamic linear swell meter
cup assembly at desired temperature, and their swellings have
been recorded versus time. The anti-swelling ability of 3. Results and discussion
KETALO15 has been compared by that of potassium chloride at
low temperature. On the other hand, the performance of 3.1. Bentonite hydration inhibition test
KETALO15 has been investigated in different formulated drilling
fluids at elevated temperature. The effect of KETALO15 on the filtration and rheological
properties (i.e. apparent viscosity (AV), plastic viscosity (PV) and
2.2.6. Wettability alteration test yield point (YP)) of aqueous bentonite dispersion has been
Some shale stabilizers can change the clay minerals surface investigated and results have been shown in Fig. 3. In the
wettability properties from hydrophilic to hydrophobic state; absence of KETALO15, bentonite particles have been well hy-
that is why this test has been employed. In this test, the pro- drated in the aqueous mediums, resulting in high AV, PV and YP
cedure illustrated by Wu [17] has been employed (Fig. 2A), which and low filtration volume.
uses smeary glass microscopic slides to the homogeneous When KETALO15 was added to the medium, even at low
bentonite-water dispersions (2 wt% bentonite) with and without concentration of 0.5 wt%, bentonite hydration has been retarded,
KETALO15 (2 and 0 wt%, respectively). Then, the water droplet and the rheological properties are very low along with high
contact angle on the prepared air-dried glass slides (Fig. 2B) has filtration volume. In KETALO15 concentrations greater than 2 wt
been measured at atmospheric conditions by automatic Atten- %, the aqueous medium inhibition potency has not improved
sion theta optical tensiometer (Biolin Scientific Instrument significantly. When potassium chloride with 2 wt% concentration
Company). was added into the medium, hydration potential of bentonite
particles reduced as much as when KETALO15 is added at the
2.2.7. Isothermal water adsorption same concentration. This is shows that KETALO15 has a
Tendency reduction of clay mineral surfaces to the water comparative performance with respect to potassium chloride as
molecules has a significant impact on their stability and is a common shale stabilizer and could be used in drilling fluids
needful for having a safe drilling operation through shaly during drilling operation through shaly formation.
Fig. 2. Smeary glass microscopic slides to the homogeneous bentonite-water dispersion: A) Before drying, B) After drying.
P. Barati et al. / Petroleum 3 (2017) 476e482 479
Fig. 5. Effect of KETALO15 addition on the filtration and rheological properties of base and high performance drilling fluids.
480 P. Barati et al. / Petroleum 3 (2017) 476e482
stabilizer in the drilling fluid, the shale hydration risk exists more
severely in comparison with KETALO15. At last, the effect of
KETALO15 on inhibition performance of different formulated
drilling fluid has been investigated at high temperature (Fig. 7 (B)).
Based on the results, presence of KETALO15 in both base and high
performance drilling fluids has improved the inhibition perfor-
mance of both drilling fluids, resulting in swelling reduction of
bentonite wafers by of 11% and 7%, respectively.
Fig. 7. Dynamic linear swelling test results: (A) aqueous solutions at low temper- 3.8. Zeta potential measurement test
ature of 26 C, (B) Different drilling fluid at high temperature of 65 C.
Fig. 8. Airewater droplet contact angles on the smeary air-dried glass microscopic slides to homogeneous bentoniteewater dispersion containing: (A) Distilled water, (B)
2.0 wt% KETALO15.
P. Barati et al. / Petroleum 3 (2017) 476e482 481
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